Polycrystalline Semiconductors Research Articles

Selenium-alloyed tellurium oxide for amorphous p-channel transistors.

Compared to polycrystalline semiconductors, amorphous semiconductors offer inherent cost-effective, simple and uniform manufacturing. Traditional amorphous hydrogenated Si falls short in electrical properties, necessitating the exploration of new materials. The creation of high-mobility amorphous n-type metal oxides, such as a-InGaZnO (ref. 1), and their integration into thin-film transistors (TFTs) have propelled advancements in modern large-area electronics and new-generation displays2-8. However, finding comparable p-type counterparts poses notable challenges, impeding the progress of complementary metal-oxide-semiconductor technology and integrated circuits9-11. Here we introduce a pioneering design strategy for amorphous p-type semiconductors, incorporating high-mobility tellurium within an amorphous tellurium suboxide matrix, and demonstrate its use in high-performance, stable p-channel TFTs and complementary circuits. Theoretical analysis unveils a delocalized valence band from tellurium 5p bands with shallow acceptor states, enabling excess hole doping and transport. Selenium alloying suppresses hole concentrations and facilitates the p-orbital connectivity, realizing high-performance p-channel TFTs with an average field-effect hole mobility of around 15 cm2 V-1 s-1 and on/off current ratios of 106-107, along with wafer-scale uniformity and long-term stabilities under bias stress and ambient ageing. This study represents a crucial stride towards establishing commercially viable amorphous p-channel TFT technology and complementary electronics in a low-cost and industry-compatible manner.

Dependence of n-Type Metal-Oxide Gas Sensor Response on the Pressure of Oxygen and Reducing Gases.

The adsorption of oxygen and its reaction with target gases are the basis of the gas detection mechanism by using metal oxides. Here, we present a theoretical analysis of the sensor response, within the ionosorption model, for an n-type polycrystalline semiconductor. Our goal of our work is to reveal the mechanisms of gas sensing from a fundamental point of view. We revisit the existing models in which the sensor response presents a power-law behavior with a reducing gas partial pressure. Then, we show, based on the Wolkenstein theory of chemisorption, that the sensor response depends not only on the reducing gas partial pressure but also on the oxygen partial pressure. We also find that the obtained sensor response does not explicitly depend on the grain size, and if it does, it is exclusively through the rate constants related to the involved reactions.

Prediction and Elucidation of Physical Properties of Polycrystalline Materials Using Multichannel Machine Learning of Electron Backscattering Diffraction

AbstractThe application of machine learning in materials science has yielded several benefits, including the prediction of physical properties and the improvement of experimental efficiency. However, with complex models, such as convolutional neural networks (CNN), learning has become a black box, from which no universal physical knowledge can be obtained. In this study, a highly accurate prediction of the electrical properties of polycrystalline semiconductor thin films is achieved by learning multichannel CNN models from electron backscattering diffraction (EBSD) data, that is band contrasts, grain boundaries, and inverse pole figures. In addition, it examines how the CNN model learned the correlation between the crystallinity, grain boundaries, crystallographic orientation, and carrier mobility by polarizing certain EBSD data and checking the predicted changes in carrier mobility. Physical parameters affecting carrier mobility can be extracted, which is challenging via human image recognition. The methods proposed in this study will not only enable the prediction of electrical properties from EBSD data for all materials but also will contribute to the discovery of complex physical phenomena beyond the limits of human analysis.

Strain-dependent grain boundary properties of n-type germanium layers

Polycrystalline Ge thin films have attracted considerable attention as potential materials for use in various electronic and optical devices. We recently developed a low-temperature solid-phase crystallization technology for a doped Ge layer and achieved the highest electron mobility in a polycrystalline Ge thin film. In this study, we investigated the effects of strain on the crystalline and electrical properties of n-type polycrystalline Ge layers. By inserting a GeOx interlayer directly under Ge and selecting substrates with different coefficients of thermal expansion, we modulated the strain in the polycrystalline Ge layer, ranging from approximately 0.6% (tensile) to − 0.8% (compressive). Compressive strain enlarged the grain size to 12 µm, but decreased the electron mobility. The temperature dependence of the electron mobility clarified that changes in the potential barrier height of the grain boundary caused this behavior. Furthermore, we revealed that the behavior of the grain boundary barrier height with respect to strain is opposite for the n- and p-types. This result strongly suggests that this phenomenon is due to the piezoelectric effect. These discoveries will provide guidelines for improving the performance of Ge devices and useful physical knowledge of various polycrystalline semiconductor thin films.

Exploring poly-crystallization in semiconductors through assumption-less growth simulations: CdTe/CdS case study

Crystal growth is a complex process with far-reaching implications for high-performance materials across various fields. Recent advancements in structural analysis methods such as polyhedral template matching, which allows semiconductor-specific analysis, coupled with simulation technology, have enabled the comprehensive study of crystallization dynamics in semiconductors. However, the exploration of polycrystalline semiconductors created with minimal external intervention of the crystallization processes is relatively uncharted in comparison with metals. In this study, we employ molecular dynamics to simulate the growth of polycrystalline CdTe/CdS with the assumptions of classical mechanics, a Stillinger–Weber potential, an amorphous substrate, and common vapor growth conditions to allow the polycrystalline structures to evolve naturally. Post-simulation, we identify and analyze impactful structures and events, comparing them to theory and experiment to gain insight into various modes of crystallization dynamics. Two research questions guided the study: (1) How realistic are assumption-less simulated polycrystalline semiconductor structures? (2) To what extent can the approach provide insight into crystallization? The simulations, performed with minimal external control, yield polycrystalline structures mirroring experimental findings. The analysis reveals key crystallization insights, such as the role of amorphous atoms in the transition from nucleation to grain growth and the transformative impact of single events, such as dislocations, on crystallization dynamics. The method paves the way for reproducing and analyzing realistic polycrystalline semiconductor structures with minimal simulation assumptions across various growth modes.

Low-temperature bonding of Si and polycrystalline diamond with ultra-low thermal boundary resistance by reactive nanolayers

Thermal management is a critical challenge in modern electronics and recent key innovations have focused on integrating diamond directly onto semiconductors for efficient cooling. However, the connection of diamond/semiconductor that can simultaneously achieve low thermal boundary resistance (TBR), minimal thermal budget, and sufficient mechanical robustness remains a formidable challenge. Here, we propose a collective wafer-level bonding technique to connect polycrystalline diamonds and semiconductors at 200 °C by reactive metallic nanolayers. The resulting silicon/diamond connections exhibited an ultra-low TBR of 9.74 m2 K GW–1, drastically outperforming conventional die-attach technologies. These connections also demonstrate superior reliability, withstanding at least 1000 thermal cycles and 1000 h of high temperature/humidity torture. These properties were affiliated with the recrystallized microstructure of the designed metallic interlayers. This demonstration represents an advancement for low-temperature and high-throughput integration of diamonds on semiconductors, potentially enabling currently thermally limited applications in electronics.

Cu2ZnSnS4 formation by laser annealing in controlled atmosphere

Laser annealing is an attractive process to form high-quality semiconductor films because of localized annealing area and short annealing time. In a previous study, a Cu2ZnSnS4 (CZTS) polycrystalline semiconductor film was realized using laser annealing in air as a light absorption layer for solar cells, although the crystallization was not sufficient in comparison with CZTS formed by the conventional thermal sulfurization process. In this study, we demonstrate a newly developed gas-atmosphere-controlled laser annealing system. A Cu–Zn–Sn–S-based precursor was formed, followed by laser annealing of the system. Laser annealing in air, Ar, and 5% H2S/Ar gas was performed to investigate the influence of the gas species on the crystallization of the precursor. A 5% H2S/Ar atmosphere promoted the crystallization of CZTS with the suppression of S desorption and Cu sulfide formation, while air and Ar atmospheres allowed the formation of Cu sulfide.

Research of the semiconductor sensors based on anomal photovoltaic effect with highly sensitive parameters of the deformation

Optical parameters of thin polycrystalline semiconductor films during deformation (t, n, 𝜆, R, T 𝑣a, 𝜑 𝜎) changes. An optical elastic effect has been created. Its physical basis is that deformation affects the shape of the zonal diagram by changing the crystal lattice constants. This condition gives rise to various optical and other electronic phenomena in semiconductor thin films .

Study of the Hydrogen Evolution Reaction on Macroscopic Snse-Based Photoelectrodes

Conversion of solar energy to valuable chemicals by using photoelectrochemical (PEC) techniques such as water splitting, carbon dioxide reduction reaction (CO2RR) and nitrogen reduction reaction (N2RR), are promising methods to solve the issues of energy crisis and global warming [1-2]. Two-dimensional (2D) and layered semiconductors, for example, transition metal chalcogenides (TMCs), metal oxides and MXenes have attracted great attention for PEC applications because of their unique properties, such as high carrier mobility, tunable bandgap, anisotropic carrier transport, and high specific surface area [3]. Our review indicates that, i) 2D and layered semiconductors can be applied for different PEC applications, both in oxidation and reduction reactions, and have ability to give higher performance in water reduction (i.e., hydrogen evolution reaction, HER) than in the other ones. ii) TMCs have been the most studied material with higher performance than the others. However, high PEC performance was achieved only on single crystal TMCs or in microelectrochemical cells, implying a limitation in the scalability of this solar energy conversion approach [4]. There is a clear need to study macroelectrodes prepared from polycrystalline semiconductors and identify the opportunities and barriers for their applications. In our study [5], tin(II) selenide (SnSe) was used as a photoelectrode for PEC HER since it has not been widely investigated for this PEC application. We fabricated SnSe macroscopic photocathodes by depositing SnSe flakes, made from commercial SnSe crystals using a liquid phase exfoliation (LPE) method, on glassy carbon. The as-received SnSe crystals were exfoliated in isopropanol/water mixtures (IPA/H2O) and pure IPA, respectively. Pure IPA was found to be the optimal solvent to prepare flakes and for achieving the highest PEC activity. An additional size separation to make three different size fractions of SnSe crystals served to further optimize the LPE process. Electrodes prepared from the largest flakes showed the highest photocurrent density of 2.44 ± 0.65 mA cm–2 at –0.74 V vs. RHE. The photodeposited Pt co-catalyst on SnSe surface further accelerated the PEC HER activity to 4.39 ± 0.15 mA cm–2. Intensity modulated photocurrent spectroscopy results manifested that the Pt co-catalyst enhanced the charge transfer process and suppressed charge carrier recombination. Overall, the solvent for exfoliation, the edge density of SnSe nanoflakes, immobilization method, and Pt co-catalyst affected the PEC HER performance of SnSe. These results indicate the merit of employing SnSe electrodes for PEC HER and inspire us to explore other photoelectrocatalytic reactions on the macroscopic exfoliated SnSe electrodes.

Polarization Alignment in Polycrystalline BiFeO3 Photoelectrodes for Tunable Band Bending.

Polarization in a semiconductor can modulate the band bending via the depolarization electric field (EdP), subsequently tuning the charge separation and transfer (CST) process in photoelectrodes. However, the random orientation of dipole moments in many polycrystalline semiconductor photoelectrodes leads to negligible polarization effect. How to effectively align the dipole moments in polycrystalline photoelectrodes into the same direction to maximize the polarization is still to be developed. Herein, we report that the dipole moments in a ferroelectric BiFeO3 photoelectrode can be controlled under external poling, resulting in a tunable CST efficiency. A negative bias of -40 voltage (V) poling to the photoelectrode leads to an over 110% increase of the CST efficiency, while poling at +40 V, the CST efficiency is reduced to only 41% of the original value. Furthermore, a nearly linear relationship between the external poling voltage and surface potential is discovered. The findings here provide an effective method in tuning the band bending and charge transfer of the emerging ferroelectricity driven solar energy conversion.

Development of Theoretical Model for Effective Carrier Lifetime in Polycrystalline Semiconductors

Development of Theoretical Model for Effective Carrier Lifetime in Polycrystalline Semiconductors

Classical modeling of extrinsic degradation in polycrystalline perovskite solar cells; defect induced degradation

In the realm of photovoltaic devices, the future appears bright for polycrystalline perovskite solar cells. However, the promise of their efficiency is threatened by a myriad of degradation mechanisms. These mechanisms, like dark spots on a sunny day, create shadows of uncertainty on the performance of polycrystalline PSCs. Nonetheless, this article comprehensively explains these degradation mechanisms and their impact on grain boundaries in PSCs. The paper investigates grain boundaries’ effects on carrier lifetime by employing various models, such as the Matthiessen rule and the Drude–Smith method. The findings reveal that defect density is the primary factor affecting the material’s performance, and grain boundaries’ size influences its changes. Drude–Smith’s model provides a more precise estimation of the mobility, total scattering lifetime, and PL quantum yield in polycrystalline semiconductors with reduced scattering time. The presented method is verified by feeding extracted parameters into Drift-Diffusion equations and fitting them with reported experimental photovoltaic conversion efficiency data. Furthermore, based on the simulation results and the strong correlation between grain boundaries and the time factor, the study proposes a comprehensive model that can effectively predict PSCs’ degradation time.

Intrinsic defects generated by iodine during TiO2 crystallization and its relationship with electrical conductivity and photoactivity

AbstractDefect formation during synthesis is one of the strategies used to improve the photoactivity of polycrystalline semiconductors such as titanium dioxide (TiO2). Defects can modify the electronic structure of TiO2 and change the surface of the interaction between the photocatalyst and the reactants. In this study, TiO2 relationship between processing in the presence of iodine and the consequent formation of intrinsic defects were explored. TiO2 nanoparticles were synthesized using the polymeric precursor method and exposed to iodine ions at concentrations up to 5 mol%. After calcination at 350°C, detailed chemical analyses revealed that iodine was absent in the samples. However, the TiO2 properties, such as specific surface area, crystallite sizes, and specific grain boundary area, were affected. Further experiments, such as electron paramagnetic resonance, diffuse reflectance, optical measurements, and electrochemical impedance spectroscopy indicated the presence of defects in the iodine‐processed samples. These defects directly influenced the electrical properties of the material, which affected the photoactivity, measured by the degradation of acetaminophen.

Magnetic-field-enhanced high thermoelectric performance in narrow-band-gap polycrystalline semiconductor Ag2+δTe

Ag2Te is a promising near-room-temperature thermoelectric material. However, its thermoelectric performance is difficult to be further improved by traditional strategies, such as doping and alloying. Herein, we demonstrate that the magnetic field is effective to enhance the thermoelectric performance of polycrystalline Ag2+δTe. The ZT of Ag2+δTe at 300 K can increase from 0.44 to 0.80 under a perpendicular magnetic field of 5 T. Similar to the magneto-thermoelectric properties observed in the semimetal materials, our studies not only reveal that the linear energy dispersion plays an important role for the increase of ZT in polycrystalline Ag2+δTe, but also suggest that external field regulation can be an effective strategy to enhance the thermoelectric properties.

Optical Properties of Reactive RF Magnetron Sputtered Polycrystalline Cu3N Thin Films Determined by UV/Visible/NIR Spectroscopic Ellipsometry: An Eco-Friendly Solar Light Absorber

Copper nitride (Cu3N), a metastable poly-crystalline semiconductor material with reasonably high stability at room temperature, is receiving much attention as a very promising next-generation, earth-abundant, thin film solar light absorber. Its non-toxicity, on the other hand, makes it a very attractive eco-friendly (greener from an environmental standpoint) semiconducting material. In the present investigation, Cu3N thin films were successfully grown by employing reactive radio-frequency magnetron sputtering at room temperature with an RF-power of 50 W, total working gas pressure of 0.5Pa, and partial nitrogen pressures of 0.8 and 1.0, respectively, onto glass substrates. We investigated how argon affected the optical properties of the thin films of Cu3N, with the aim of achieving a low-cost solar light absorber material with the essential characteristics that are needed to replace the more common silicon that is currently in present solar cells. Variable angle spectroscopic ellipsometry measurements were taken at three different angles, 50∘, 60∘, and 70∘, to determine the two ellipsometric parameters psi, ψ, and delta, Δ. The bulk planar Cu3N layer was characterized by a one-dimensional graded index model together with the combination of a Tauc–Lorentz oscillator, while a Bruggeman effective medium approximation model with a 50% air void was adopted in order to account for the existing surface roughness layer. In addition, the optical properties, such as the energy band gap, refractive index, extinction coefficient, and absorption coefficient, were all accurately found to highlight the true potential of this particular material as a solar light absorber within a photovoltaic device. The direct and indirect band gap energies were precisely computed, and it was found that they fell within the useful energy ranges of 2.14–2.25 eV and 1.45–1.71 eV, respectively. The atomic structure, morphology, and chemical composition of the Cu3N thin films were analyzed using X-ray diffraction, atomic force microscopy, and energy-dispersive X-ray spectroscopy, respectively. The Cu3N thin layer thickness, profile texture, and surface topography of the Cu3N material were characterized using scanning electron microscopy.

Local symmetry breaking drives picosecond spin domain formation in polycrystalline halide perovskite films.

Photoinduced spin-charge interconversion in semiconductors with spin-orbit coupling could provide a route to optically addressable spintronics without the use of external magnetic fields. However, in structurally disordered polycrystalline semiconductors, which are being widely explored for device applications, the presence and role of spin-associated charge currents remains unclear. Here, using femtosecond circular-polarization-resolved pump-probe microscopy on polycrystalline halide perovskite thin films, we observe the photoinduced ultrafast formation of spin domains on the micrometre scale formed through lateral spin currents. Micrometre-scale variations in the intensity of optical second-harmonic generation and vertical piezoresponse suggest that the spin-domain formation is driven by the presence of strong local inversion symmetry breaking via structural disorder. We propose that this leads to spatially varying Rashba-like spin textures that drive spin-momentum-locked currents, leading to local spin accumulation. Ultrafast spin-domain formation in polycrystalline halide perovskite films provides an optically addressable platform for nanoscale spin-device physics.

The effect of sulfur precursor on the morphology, properties and formation mechanism of chemical bath deposited Pb1+xS thin solid films

Pb1+хS thin films of 190–360 nm thickness have been synthesized on glass substrates by chemical bath deposition from aqueous solutions using different thioamides (thiourea, N-allylthiourea, thioacetamide) as sulfur precursors. The obtained films are polycrystalline semiconductors with n-type conductivity. The effect of the sulfur origin on the crystalline structure, morphology and formation mechanism of Pb1+хS thin films is analyzed. The formal rate constants of Pb1+хS formation reactions are determined. Quantum-chemical calculations approve that a lead superstoichiometry in the obtained films may be attributed to types of point defects: atomic vacancies in the sulfur sublattice and the lead doping the sulfur sublattice. A correlation is established between the amount of lead excess and the optical band gap of Pb1+хS: the greater the excess of lead is, the wider the band gap is. The fractal analysis of Pb1+хS thin films evidences the film growth obeying model of a cluster-by-cluster association in three-dimensional space.

Realizing the heteromorphic superlattice: Repeated heterolayers of amorphous insulator and polycrystalline semiconductor with minimal interface defects.

An unconventional "heteromorphic" superlattice (HSL) is realized, comprised of repeated layers of different materials with differing morphologies: semiconducting pc-In2 O3 layers interleaved with insulating a-MoO3 layers. Originally proposed by Tsu in 1989, yet never fully realized, the high quality of the HSL heterostructure demonstrated here validates the intuition of Tsu, whereby the flexibility of the bond angle in the amorphous phase and the passivation effect of the oxide at interfacial bonds serve to create smooth, high-mobility interfaces. The alternating amorphous layers prevent strain accumulation in the polycrystalline layers while suppressing defect propagation across the HSL. For the HSL with 7:7nm layer thickness, the observed electron mobility of 71 cm2 /Vs, matches that of the highest quality In2 O3 thin films. The atomic structure and electronic properties of crystalline In2 O3 / amorphous MoO3 interfaces are verified using ab-initio molecular dynamics simulations and hybrid functional calculations. This work generalizes the superlattice concept to an entirely new paradigm of morphological combinations. This article is protected by copyright. All rights reserved.

Surface potential variation across (hk1) and non-(hk1) grain boundaries of antimony triselenide

Electronic materials that can tolerate defects or create self-passivated interfaces expand the horizons to more sustainable electronic devices. Two heuristic models suggest that (i) antimony triselenide is a defect tolerant semiconductor (to certain point defects) and that (ii) the boundaries of grains with a specific orientation are self-passivated. Yet, experimental support or scrutiny of these models is lacking. Partly because measuring a passive quality of a material is perplexing. A possible way forward is to measure defect activity in correlation with other experimental evidence for defect presence, for example, by relating the grain boundaries’ (GBs) nanostructure and electronic quality. One measure of the electronic quality is the magnitude of the surface potential variation across grain boundaries—a high (charged) defect concentration and low defect tolerance typically leads to a significant surface potential variation. On the other hand, direct observation of defects (e.g., by electron microscopy) and a small surface potential variation indicates that the material is defect tolerant. In parallel, a comparison of the surface potential variation across grain boundaries in films with grains of different orientations provides a qualitative measure of the self-passivation of material because only certain crystallographic surfaces are expected to be self-passivated. Herein we report that regardless of the grains’ mutual respective orientation, the grain boundaries of antimony triselenide have a relatively benign electronic quality. This is evident in a shallow surface potential variation across grain boundaries (10–50 mV; 195 GBs were investigated). Yet, a high-resolution TEM investigation reveals that a variety of defects is prevalent at and near the GBs. Additionally, we found that GBs in films with distinct (hk1) orientation indeed have a lower surface potential variation than grains with (hk0) orientation. These findings support both heuristic models and provide a practical way to scrutinize defect tolerance in other polycrystalline semiconductors.

N-Type Polycrystalline Germanium Layers Formed by Impurity-Doped Solid-Phase Growth

The carrier mobility of polycrystalline Ge thin-film transistors has significantly improved in recent years, raising hopes for the realization of next-generation electronic devices. Here, we adapted advanced solid-phase crystallization, which achieved the highest hole mobility of the polycrystalline semiconductor layer, to Ge layers doped with n-type impurities (P, As, and Sb). The type and amount of dopants had marked effects on the growth morphology and electrical properties of the Ge layers because they altered the activation energies in crystal growth, dopant activation rates, and grain boundary properties. In particular, P doping was effective in increasing the grain size (25 μm) and lowering the grain boundary barrier height (20 meV), which improved the electron concentration (8.0 × 1018 cm–3) and electron mobility (380 cm2 V–1 s–1) in n-type polycrystalline Ge layers. The electron mobility is greater than that of most semiconductor layers synthesized at low temperatures (≤500 °C) on insulators, and this will pave the way for advanced electronic devices, such as multifunctional displays and three-dimensional large-scale integrated circuits.